Ethers of tertiary-alkyl phenylphenols



Patented June 6, 1939 UNITED STATES PATENT" OFFICE ETHERS OFTERTIARY-ALKYL PHENYLPHENOLS Gerald H. Coleman and Garnett V. Moore,Midland, Mich., assignors to The Dow Chemical Company, Midland, Mich., acorporation of Michigan No Drawing. Application May 31, 1938, Serial No.211,025

8 Claims.

tertiary-alkyl phenylphenols are Viscous, waterwhite liquids orlow-melting solids having utility as plasticizers, solubilizing agents,lubricants, insecticides, and intermediates. These compounds 10 aresubstantially insoluble in water, soluble in most common organicsolvents, resistant to decomposition by heat and discoloration by light,and characterized by high boiling points and low volatilities. Theinvention, then, consists in the new compounds and compositionscomprising the same hereinafter described and particularly pointed outthe claims. he ethers of the tertiary-alkyl-phenylphenols 3 be preparedby heating an alcoholic or aqueous alcoholic solution of an alkali metaltertiaryalkyl-p-henylphenolate with an alkyl halide to a temperature atwhich reaction occurs, and thereafter separating the desired etherproduct from the reacted mixture as. by fractional distillation,

etc. The tertiary-alkyl-phenylphenolate and alkyl halide may be employedin any desired proportions, although we' generally employ a slightmolecular excess of alkyl halide. While the process can be carried outby refluxing the phenolate solution and alkyl halide mixture underatmospheric pressure, we generally prefer to introduce the reactantsinto a suitable pressure, reactor equipped with means for agitation andthereafter to carry out the reaction at temperatures between about 100and 180 C. and under autogenous pressure. The etherification isordinarily complete in from 1 to 6 hours, after which the reactedmixture is diluted with water to separate out the 41' crude etherproduct as an immiscible oil. This oil is separated and washed with anaqueous-alcoholic solution of potassium or sodium hydroxide to recoverunreacted phenols, and the residue from the extraction thereafter washedwith water, 4'5 dried, and fractionally distilled under reduced pressureto obtain the desired ethers in substantially pure form.

The tertiary-alkyl-phenylphenols employed in the reaction may beprepared by the condensation of tertiary-alkyl olefines, halides oralcohols, with the phenylphenols in the presence of a suitable FriedelCrafts catalyst substantially as described in United States applicationSerial No. 78,640, filed May 8, 1936", for Branched-chainalkyl-phenylphenols. In preparing tertiaryalkyl substitutedphenylphenols according to this method, the reaction is convenientlycarried out in the liquid phase in the presence of the catalyst, slowlyadding the olefine, halide, or alcohol below the surface of the moltenphenolic reaction mix- 5.;

ture with stirring, and thereafter heating and stirring the reactionmixture until the condensation is complete. The reaction temperature isusually between about and 175 C., although higher temperatures may beemployed. If desired, the 10,;

reactants may be dispersed in an inert solvent, e. g. carbontetrachloride, ethylenechloride, etc., in which case the use of somewhatlower reaction temperatures is practicable. After the reaction iscompleted, the crude alkylated mixture is 15.

washed with dilute aqueous hydrochloric acid to decompose and removeresidual catalyst, and the tertiary-alkyl-phenylpheno1 separated as byfractional distillation in vacuo. In place of the phenylphenols,mono-alkyl phenylphenols may also be employed as starting materials inthe reaction. The term tertiary-alkyl-p henylphenols as employed in thespecification and claims of this application includespoly-alkyl-phenylphenols in which all of the alkyl groups are nottertiary in configuration, provided only that at least onetertiary-alkyl radical beattached to the hydroxylated benzene ring ofthe phenylphenol nucleus. Included also within the scope of theinvention are ethers of those phenylphenol compounds containing halogensubstituents in the oxygenated benzene ring as well as thetertiary-alkyl group.

The following examples describe the preparation of certain of our newether compounds, but are not to be construed as limiting the invention:35

- EXAMPLE 1 Normal-butyl ether of 4-tertiary-butyl-6-phenylphenol 113grams (0.5 mol) of 4-tertiary-butyl-6-phen- 40 ylphenol was dissolved inmilliliters of methyl alcohol and a solution of 20 grams (0.5 mol) ofsodium hydroxide in 20 milliliters of water and 50 milliliters of methylalcohol added thereto to form an aqueous alcoholic solution of sodium-45 4-tertiary-butyl-B-phenylphenolate. This solution was poured into apressure reactor equipped with an aqueous alcoholic solution ofpotassium of normal-butyl chloride added thereto. The reactor was sealedand heated at C. for 2 50' hydroxide to remove traces of unreacted4-tertiary-butyl-6-phenylphenol. The ether solution was then dried andfractionally distilled under reduced pressure, whereby there wasobtained 104.5 grams (0.371 mol) of the normal-butyl ether of4-tertiary-butyl-6-phenylphenol as a colorless oil boiling at 157-159 C.at 3 millimeters pressure, and having a specific gravity of 0.979 at20/4 C.

EXAMPLE 2 Isopropyl ether of 3-phenyZ4-tertiarybutyl phenol In a similarmanner, 0.5 mol of sodium-3- phenyl-Q-tertiary-butyl phenolate wasreacted with approximately 0.75 mol of isopropyl chloride, whereby therewas obtained the isopropyl ether of 3-phenyl-4-tertiary-butyl phenol asa colorless, viscous oil boiling at 164-168 C. at 3 millimeterspressure, and having the specific gravity 0.990 at 20/4 C.

In a similar manner, other tertiary-alkyl phenyl phenols, tertiary alkylhalo phenylphenols, and poly-alkyl phenylphenols containing at least onetertiary-alkyl group attached to the hydroxylated benzene nucleus werereacted with various alkyl halides to produce compounds of which thefollowing are representative:

The ethyl ether of 2,4-di-tertiary-butyl-6'- .phenyl-phenol, a thick,viscous oil boiling at 176-179 C. at 4 millimeters pressure, and havinga specific gravity of 0.973 at 20/4 C. On standing, this compound showeda tendency to crystallize.

The ethyl ether of 4-tertiary-hexyl-6-phenylphenol, a colorless oilboiling at 150-153 C. at 3 millimeters pressure, and having the specificgravity 0.988 at 20/4 C.

The ethyl ether of 4tertiary-amyl-6-phenylphenol, a waterwhite, sirupyliquid boiling at 145-149 C. at 3 millimeters pressure, and having aspecific gravity of 0.996 at 20/4 C.

The ethyl ether of 4-tertiary-butyl-6-phenylphenol, a mobile, colorlessliquid boiling at 140-144 C. at 3 millimeters pressure, and having aspecific gravity of 1.00 at 20 /4 C.

The normal-amyl ether of 4-tertiary-butyl-6- phenylphenol, a viscous,water-white liquid boiling at 174-l77 C. at 4 millimeters pressure, andhaving a specific gravity of 0.972 at -20/4 C.

Other ether compounds which can be prepared in a like manner by reactingtogether alkyl halides and tertiary-alkylated phenylphenols other thanthose shown in the examples include methyl ether of4-tertiary-butyl-fi-phenylphenol, ethyl ether of4-tertiary-octyl-G-phenylphenol, ethyl ether of2-ch1oro-4-tertiary-butyl6-phenylphenol, ethyl ether of2-bromo-4-tertiary-amyl-G-phenylphen01, ethyl ether of2-tertiary-butyl-G-phenylphenol, ethyl ether of2-methyl-4-tertiary-butyl-6- phenylphenol, ethyl ether of2-tertiary-butyl-4- phenylphenol, ethyl ether oftertiary-butyl-monoiodo-fi-phenylphenol, isobutyl ether of2-tertiaryamyl-5-phenylphenol, secondary-amyl ether of 4-tertiary-octyl-G-phenylphenol, normal-octyl ether of4-tertiary-butyl6-phenylphenol, tertiary-butyl ether of4-tertiary-butyl-G-phenylphenol, and the like.

Certain of the compounds described in the foregoing examples have beentested by the Fest- Grady method (Soap, 8, No. 4, 1932) and found to beparticularly valuable as fly toXics. For example, a 3 per cent solutionof the ethyl ether of 4-tertiary-butyl-G-phenylphenol in kerosene,

when tested against house flies, was found to give an excess of an 80per cent knockdown within ten minutes. The ethers were also found tohave utility as plasticizers and modifying agents for polystyrene andcellulose ether plastic compositions.

Other modes of applying the principle of our invention may be employedinstead of those explained, change being made as regards the materialsemployed, provided the products described in the following claims hethereby obtained.

We therefore particularly point out and distinctly claim as ourinvention:

1. An alkyl ether of an alklated phenylphenol wherein at least onetertiary-alkyl radical is attached to the oxygenated benzene ring.

2. An alkyl ether of an alkylated phenylphenol wherein at least onetertiary-alkyl radical is attached to the oxygenated benzene ring, andeach such alkyl group contains not more than 8 carbon atoms.

3. An ethyl ether of an alkylated phenylphenol wherein at least onetertiary-alkyl radical is attached to the oxygenated benzene ring.

4. A compound having the formula wherein R represents a tertiary-alkylgroup, and n represents an integer.

5. A compound having the formula wherein R represents a tertiary-alkylgroup con taining from 4 to 8 carbon atoms, inclusive, and n representsan integer from 1 to 8, inclusive.

6. A compound having the formula wherein R represents a tertiary-alkylgroup containing from 4 to 8 carbon atoms, inclusive, and n representsan integer from 1 to 8, inclusive,

7. A compound having the formula wherein R represents a tertiary-alkylgroup containing from 4 to 8 carbon atoms, inclusive.

8. A compound having the formula /CH3 QJ- CCHs wherein n represents aninteger from 1 t0 8, inelusive.

GERALD H. COLEMAN. GARNETT V. MOORE.

CERTIFICATE OF CORRECTION. Patent No. 2,161, 558.; June 6, 1959.

A GERALD H. COLEMAN, ET AL.

and column, line 1+8, for the words "an aqueous alcoholic solution ofpotassium" read means for agitation and 1 .6.5 grams (0.5 mol) and thatthe Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

